Page 54 - 《精细化工》2020年第4期

·688· 精细化工 FINE CHEMICALS 第 37 卷

表 1 LMOFs 检测有机农药的拟合数据 frameworks[J]. Chemical Reviews, 2012, 112(2): 1126-1162.
Table 1 Fitting parameters for detection of organic pesticides [8] HU Z, DEIBERT B J, LI J. Luminescent metal-organic frameworks
for chemical sensing and explosive detection[J]. Chemical Society
by LMOFs Reviews, 2014, 43(16): 5815-5840.
[9] SUN C Y, WANG X L, ZHANG X, et al. Efficient and tunable
K SV/ Standard 2
λ ex
λ em
ƒ 1 ƒ 2 r white-light emission of metal-organic frameworks by iridium-
/nm /nm (L/μmol) error
complex encapsulation[J]. Nature Communications,2013, 4: 2717.
LMOF-1+TFL 360 423 1.19 –0.19 2.595 0.488 0.989 [10] ZHOU Y, YAN B. Lanthanides post-functionalized nanocrystalline
metal-organic frameworks for tunable white-light emission and
LMOF-2+TFL 360 453 1.22 –0.22 0.686 0.153 0.989 orthogonal multi-readout thermometry[J]. Nanoscale, 2015, 7(9):
LMOF-1+NF 360 423 1.09 –0.09 0.281 0.034 0.992 4063-4069.
[11] LI Y, TANG J, HE L, et al. Core-shell upconversion nanoparticle@metal-
LMOF-2+NF 360 453 1.30 –0.30 0.066 0.017 0.985 organic framework nanoprobes for luminescent/magnetic dual-mode
targeted imaging[J]. Advanced Materials, 2015, 27(27): 4075-4080.
利用式（2）计算 LMOF-1 及 LMOF-2 对 TFL [12] MCKINLAY A C, MORRIS R E, HORCAJADA P, et al. BioMOFs:
metal-organic frameworks for biological and medical applications[J].
及 NF 的最低检测限（LOD） [30] 。 Angewandte Chemie International Edition, 2010, 49(36): 6260-6266.
–3
LOD=(S/N)×10 /K SV （2） [13] ZHANG X, WANG W, HU Z, et al. Coordination polymers for
energy transfer: Preparations, properties, sensing applications, and persp-
式中：S/N 为信噪比，数值为 16380。 ectives[J]. Coordination Chemistry Reviews, 2015, 284: 206-235.
[14] CHE X J, HOU S L, SHI Y, et al. Selectively detecting toluene and
LMOF-1 对 TFL 及 NF 的 LOD 数值分别为 5.54 benzaldehyde by two stable lanthanide-organic frameworks as
luminescent probes[J]. Dalton Transactions, 2019, 48(10): 3453-3458.
及 58.29 μmol/L；LMOF-2 对 TFL 及 NF 的 LOD 数 [15] ZHAO M, HUANG Y, PENG Y, et al. Two-dimensional metal-
值分别为 23.88 及 248.18 μmol/L。 organic framework nanosheets: Synthesis and applications[J].
Chemical Society Reviews, 2018, 47(16): 6267-6295.
[16] LIU X J, ZHANG Y H, CHANG Z, et al. A water-stable metal-
3 结论 organic framework with a double-helical structure for fluorescent
sensing[J]. Inorganic Chemistry, 2016, 55(15): 7326-7328.
[17] KUMAR P, PAUL A K, DEEP A. A luminescent nanocrystal metal
采用富电子的三嗪类配体，通过水热法合成了 organic framework for chemosensing of nitro group containing organo-
phosphate pesticides[J]. Analytical Methods, 2014, 6(12): 4095-4101.
2 种发光金属有机框架 LMOF-1 及 LMOF-2，并将 [18] KRENO L E, LEONG K, FARHA O K, et al. Metal-organic
它们作为荧光探针用于检测 TFL 及 NF。结果表明： framework materials as chemical sensors[J]. Chemical Reviews,
2012, 112(2): 1105-1125.
（1）通过实验结果及 DFT 计算证实，LMOFs 对 TFL [19] TAYLOR J M, DAWSON K W, SHIMIZU G K. A water-stable
metal-organic framework with highly acidic pores for proton-conducting
的检测机理同时包括电荷转移机理及荧光共振能量 applications[J]. Journal of the American Chemical Society, 2013,
转移机理，而 LMOFs 对 NF 的检测机理仅为电荷转 135(4): 1193-1196.
[20] LIU B. Metal-organic framework-based devices: Separation and sensors
移机理。（2）LMOF-1 对 TFL 及 NF 的检测效率分 [J]. Journal of Materials Chemistry, 2012, 22(20): 10094-10101.
[21] TAYLOR J M, DAWSON K W, SHIMIZU G K H. A water-stable
别为（2.595±0.488）及（0.281±0.034） L/μmol； metal- organic framework with highly acidic pores for
LMOF-2 对 TFL 及 NF 的检测效率分别为（0.686± proton-conducting applications[J]. Journal of the American Chemical
Society, 2013, 135(4): 1193-1196.
0.153）及（0.066±0.017） L/μmol；LMOF-1 对 TFL [22] FANG Q R, ZHU G S, JIN Z, et al. Mesoporous metal-organic
framework with rare etb topology for hydrogen storage and dye
具有最低的检测限，为 5.54 μmol/L。以上研究为开 assembly[J]. Angewandte Chemie International Edition, 2007,
发高效、快速、便捷的有机农药检测技术提供了理 119(35): 6758-6762.
[23] ZHANG L, KANG Z, XIN X, et al. Metal-organic frameworks based
论依据及实验参考。 luminescent materials for nitroaromatics sensing[J]. Cryst Eng Comm,
2016, 18(2): 193-206.
参考文献: [24] AZHAR M R, ABID H R, SUN H, et al. Excellent performance of
copper based metal organic framework in adsorptive removal of toxic
[1] SU H, LIN Y, WANG Z, et al. Magnetic metal-organic framework- sulfonamide antibiotics from wastewater[J]. Journal of Colloid and
titanium dioxide nanocomposite as adsorbent in the magnetic solid- Interface Science, 2016, 478: 344-352.
phase extraction of fungicides from environmental water samples[J]. [25] SU H, LIN Y, WANG Z, et al. Magnetic metal-organic framework-
Journal of Chromatography A, 2016, 1466: 21-28. titanium dioxide nanocomposite as adsorbent in the magnetic solid-
[2] LI S, ZHANG X, HUANG Y. Zeolitic imidazolate framework-8 phase extraction of fungicides from environmental water samples[J].
derived nanoporous carbon as an effective and recyclable adsorbent Journal of Chromatography A, 2016, 1466: 21-28.
for removal of ciprofloxacin antibiotics from water[J]. Journal of [26] DI L, ZHANG J J, LIU S Q, et al. Two dynamic abw-type metal
2+
Hazardous Materials, 2017, 321: 711-719. organic frameworks built of pentacarboxylate and Zn as photo-
[3] RAGHU P, KUMARA SWAMY B E, MADHUSUDANA R T, et al. luminescent probes of nitroaromatics[J]. Crystal Growth & Design,
Sol-gel immobilized biosensor for the detection of organophos- 2016, 16(8): 4539-4546.
phorous pesticides: A voltammetric method[J]. Bioelectrochemistry, [27] SINGHA D K, MAJEE P, MANDAL S, et al. Detection of pesticides
2012, 83: 19-24. in aqueous medium and in fruit extracts using a three-dimensional
[4] MALIK A K, FAUBEL W. A review of analysis of pesticides using metal-organic framework: Experimental and computational study[J].
capillary electrophoresis[J]. Critical Reviews in Analytical Chemistry, Inorganic Chemistry, 2018, 57(19): 12155-12165.
2001, 31(3): 223-279. [28] NAGARKAR S S, JOARDER B, CHAUDHARI A K, et al. Highly
[5] CHEN Y, LOPEZ S, HAYWARD D G，et al. Determination of selective detection of nitro explosives by a luminescent metal-
multiresidue pesticides in botanical dietary supplements using gas organic framework[J]. Angewandte Chemie International Edition,
chromatography-triple-quadrupole mass spectrometry (GC-MS/MS)[J]. 2013, 52(10): 2881-2885.
Journal of Agricultural and Food Chemistry, 2016, 64(31): 6125- [29] DI L, XING Y, WANG X, et al. The influence of molecular structure
6132. on collision radius for optical sensing of molecular oxygen based on
[6] XU N, ZHANG Q, HOU B, et al. A novel magnesium metal-organic cyclometalated Ir(Ⅲ) complexes[J]. RSC Advances, 2018, 8(71):
framework as a multiresponsive luminescent sensor for Fe(Ⅲ) ions, 41040-41047.
pesticides, and antibiotics with high selectivity and sensitivity[J]. [30] WANG X D, WOLFBEIS O S. Optical methods for sensing and
Inorganic Chemistry, 2018, 57(21): 13330-13340. imaging oxygen: Materials, spectroscopies and applications[J].
[7] CUI Y, YUE Y, QIAN G, et al. Luminescent functional metal-organic Chemical Society Reviews, 2014, 43(10): 3666-3761.